Process for shrinkproofing wool and resultant product

ABSTRACT

WOOL IS RENDERED SHRINK RESISTANT BY TREATING IT WITH A SOLUTION CONTAINING A POLYHYDROXIDE-MODIFIED ISOCYANATE AND, THEREAFTER, CURING THE THUS-TREATED WOOL WITH WATER. THE POLYHYDROXIDE-MODIFIED ISOCYANATE USED CONTAINS AT LEAST 3 FREE NCO GROUPS PER MOLECULE. THE PREFERRED ISOCYANATE MATERIALS IS TOLUENE DIISOCYANATE AND TYPICAL POLYHYDROXY COMPOUNDS WHICH MAY BE REACTED WITH IT TO EFFECT ITS MODIFICATION ARE CASTOR OIL, GLYCERINE AND TRIMETHVIOL PROPANE.

United States Patent US. Cl. 117-62.2 16 Claims ABSTRACT OF THE DISCLOSURE Wool is rendered shrink resistant by treating it with a solution containing a polyhydroxide-modified isocyanate and, thereafter, curing the thus-treated wool with water. The polyhydroxide-modified isocyanate used contains at least 3 free NCO groups per molecule. The preferred isocyanate material is toluene diisocyanate and typical polyhydroxy compounds which may be reacted with it to effect its modification are castor oil, glycerine and trimethylol propane.

This is a continuation-in-part of co-pending application Ser. No. 814,846, filed Apr. 9, 1969, now abandoned, which is in turn a continuation-in-part of application Ser. No. 510,102, filed Nov. 26, 1965, now abandoned.

This invention relates to an improved composition and process for treating wool and more particularly it relates to an improved composition and process for treating wool and similar proteinaceous materials so as to render such materials substantially shrinkproof.

In the past, a great deal of effort has been expended in attempts to develop compositions and processes for treating wool and similar proteinaceous materials so as to render such materials resistant to shrinking during washing. This has been particularly true in recent years with the advent of various so-called synthetic wools, such as the polyester fibers, or polyacrylic fibers, and the like, which materials may be laundered repeatedly without encountering a problem of shrinking.

In general, the prior treatments proposed to shrinkproof wool have involved the use of materials which form a coating on the wool fibers, thereby minimizing the effect of the overlapping scales of the fiber or of materials which react with and chemically modify the wool fibers themselves, thus modifying or degrading these scales. For the most part, these prior art treatments have not been satisfactory because they have been difiicult or expensive to apply or have not had sufiicient durability to make the treated fabric substantially permanently shrink resistant. An additional, and perhaps a major, disadvantage of these prior art treatments has been that they frequently have an adverse effect on the hand or feel of the fabrics with which they are treated. Thus, wool and similar proteinaceous materials which have heretofore been treated to render them shrinkproof often become hard, and/ or stiff and boardy as a result of these treatments. Accordingly, up to the present time, there has not been available a satisfactory process for treating wool and similar proteinaceous fibers to render them substantially permanently shrinkproof.

It is, therefore, an object of the present invention to provide an improved process for treating wool and other proteinaceous materials so as to render them substantially permanently shrinkproof, which process is easily and economically carried out.

These and other objects of the present invention will become apparent to those skilled in the art from the description which follows.

Pursuant to the above objects, the present invention includes a process for treating a proteinaceous material which comprises contacting the proteinaceous material with a polymerizable treating solution comprising a polyhydroxy-modified isocyanate composition containing from 3 to 6 free NCO groups per molecule. Thereafter, the thus-contacted material is cured with water. Preferably, the polyhydroxy-modified isocyanate composition in the polymerizable treating solution is the reaction product of a polyhydroxy compound containing 3 to 6 hydroxyl groups and a diisocyanate, the reactants being in the ratio of about one mole of polyhydroxy compound to 3 to 6 moles of diisocyanate.

More specifically, in the practice of the present invention, the proteinaceous materials to be treated are proteinaceous textile materials, and particularly proteinaceous textiles which undergo shrinking during normal laundering operations. These textile materials may be in various forms, including yard goods, as well as various finished articles, such as articles of clothing, including coats, sweaters, socks, shirts, trousers, skirts, and the like. Of the numerous proteinaceous materials of which such articles may be made, the process of the present invention has been found to be particularly applicable in the treatment of wool. Accordingly, hereinafter, primary reference will be made to wool as being the preferred proteinaceous material. This is not, however, to be taken as a limitation on the present invention as other proteinaceous materials which are subject to shrinkage may also be advantageously treated by the present process, including fabrics made of alpaca, angora, camel hair, cashmere, huarizo, llama, misti, mohair, suri, vicuna, and the like. Additionally, the process of the present invention is not limited to the treatment of Wool or other proteinaceous materials, in the form of yard goods or finished articles, but may in many instances also be utilized in treating these materials in the fiber or yarn form. It is to be further appreciated that the proteinaceous materials treated may be admixed with other non-proteinaceous materials as in various fiber blends with synthetics or other natural fiber materials or they may be in the form of a so-called multi-ply fabric wherein the proteinaceous fabric is bonded to a fabric of some other material, such as acetate, rayon, nylon, and the like. The treatment of these latter types of material has been found to be particularly advantageous in that such materials when treated are found to be substantially wrinkle-free after washing, thereby providing a wash and wear wool.

In treating a proteinaceous textile material so as to make it shrink resistant, the material is impregnated with a solution which comprises as the essential sh-rinkproofing component, a modified diisocyanate compound, the diisocyanate being modified by being reacted with a polyhydroxy material containing from 3 to 6 hydroxyl groups, so that the resulting modified diisocyanate contains from about 3 to 6 free NCO groups. Illustrative of the polyhydroxy compounds containing 3 to 6 hydroxyl groups, with which the diisocyanate may be modified are polyhydric aclohols containing 3 to 6 hydroxyl groups, glycerides of hydroxy acids, sugars containing 3 to 6 hydroxyl groups and alkyl and aralkyl polyhydroxy acids, ethers, aldehydes and ketones containing 3 to 6 hydroxyl groups. These materials may contain one or more dissimilar atoms between carbon atoms, such as oxygen, sulfur, and the like, and may be substituted with non-interfering substituents, such as halogens, aryl, including phenyl, and the like. By non-interfering it is meant substituents having a reactivity with isocyanates which is less than that of the hydroxy groups. Generally, these compounds will contain from about 3 to about carbon atoms in a straight or branched chain and may be saturated or unsaturated, i.e., contain one or more double or triple bonds.

Exemplary of polyhydric alcohols which may be used are pentaerythritol, dipentaerythritol, trimethylol propane, trimethylol ethane, trimethylol butane, trimethylol isobutane, trimethylol pentane, trimethylol hexane, trimethylol butene, trimethylol pentene, glycerol, sorbitol, ane, trimethylol heptadecane, trirnethylol propene, trimethylol butane, trimethylol pentene, glycerol, sorbitol, butanetriol, 1,2,3,4,5,6-hexanehexol, inositol, trimethylolpropane adipate, mannitol, methyltrimethylmethane, 1,4,6 octanetriol, 1,2,6 hexanetriol, 1,3,5 hexanetriol, polyallyl alcohol, and the like. Sugars which may be used include tetroses, pentoses, hexoses, heptoses, and the like. Tetroses (C H O include aldoses such as threose and erythrose and ketoses like erythrulose. Pentoses (C H O include aldoses and ketoses, such as arabinose, xylose, lyxose, ribose, and arabinulose. Hexoses (C H O and heptoses (C7H1407) include aldoses and ketoses such as glucose, gulose, tagatose, mannose, galactose, dextrose, talose, allose, idose, altrose, fructose, sorbose, levulose, and mannoheptose. Additionally, disaccharides of bioses, trioses and tetroses may also be used.

Exemplary of the glycerides of hydroxy acids are castor oil (glyceride of ricinoleic acid), as well as the glycerides of such acids as threonic acid, erythronic acid, glycolic acid, lactic acid, hydroxybutyric acid, hydroxy-valeric acid, cerebronic acid, hydroacrylic acid, hydroxycaproic acid, hydroxystearic acid, hydroxydecanoic acid, sabinic acid, juniperic acid, jalapinolic acid, B-hydroxyacrylic acid, a-hydroxyvinylacetic acid, ambrettolic acid, glyceric acid, 3,12-dihydroxypalmitic acid, trihydroxy n-butyric acid, trihydroxyisobutyric acid, aleuritic acid, and the like. As has been noted hereinabove, these glycerides contain 3 to 6 hydroxyl groups.

Exemplary of other polyhydroxy compounds which may be used are acids such as trihydroxy n-butyric acid, trihydroxyisocutyric acid, erythronic acid, pentahydroxycaproic acid, threonic acid, aleuritic acid, hexahydroxyheptonic acid, satinic acid, as well as the various aldonic acids including arabonic acid, xylonic acid, sibonic acid, lyxonic acid, gluconic acid, mannonic acid, galactonic acid, glulonic acid, talonic acid, idonic acid, altronic acid, allanic acid, pentahydroxypimelic acid, and the like. Other materials include ethoxylated castor oil, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, sorbitan monopalmitate, polyoxyethylene sorbitol laurate, polyoxyethylene sorbitol oleate, sorbitan sesquioleate, populin, picrocrocin, arochloralic acid, streptose, taxicatin, tetrakis (hydroxymethyl) phosphonium chloride, and the like. Of all of the above compounds, the preferred are castor oil, glycerol and trimethylol propane and hereinafter, primary reference will be made to these materials.

Various organic diisocyanates may be modified by the above polyhydroxy materials. Of the hydrocarbon polyisocyanates, the aryl and alkaryl polyisocyanates of the benzene and naphthalene series are more reactive and less toxic than the aliphatic members. Consequently, the aromatic compounds are preferred in the present invention. The preferred compounds which are at present most readily available commercially are 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof. However, others may be used, among them phenyl diisocyanate; alpha naphthyl diisocyanate; 4-tolylene diisocyanate; n-hexyl diisocyanate; methylene-bis-(4-phenyl isocyanate); 3,3 bitolylene 4,4 diisocyanate; 3,3- dimethoxy 4,4' biphenylene diisocyanate; 1,5-naphthalene diisocyanate; 2,4-chlorophenyl diisocyanate; hexamethylene diisocyanate; ethylene diisocyanate; trimethylene diisocyanate; tetramethylene diisocyanate; pentamethylene diisocyanate; decamethylene diisocyanate; 1,3- cyclopentylene diisocyanate; 1,2-cyclohexylene diisocyanate; 1,4-cyclohexylene diisocyanate; cyclopentylidene diisocyanate; cyclohexylidene diisocyanate; p-phenylene diisocyanate; m-phenylene diisocyanate; 4,4'-diphenyl propane diisocyanate; 4,4'-diphenyl methane diisocyanate; 1- methyl 2,4 phenylene diisocyanate; 4,4-diphenylene diisocyanate; 1,2-propylene diisocyanate; 1,2-butylene diisocyanate; 2,3-butylene diisocyanate; 1,3-butylene diisocyanate; ethylidene diisocyanate; propylidene diisocyanate; and butylidene diisocyanate. In addition, isothiocyanates and mixtures of isocyanates may be employed. Also contemplated are the many impure or crude polyisocyanates that are commercially available.

The preferred polyhydroxy-modified diisocyanates for use in the present process have the following generic formula:

wherein R is independently selected from alkyl groups containing from 1 to 25 carbon atoms in a straight or branched chain; or aralkyl groups containing from 8 to 30 carbon atoms in a straight or branched chain; and R' is independently selected from alkyl, alkaryl, aralkyl or aryl groups containing from 6 to 40 carbon atoms, in a straight or branched chain.

It is to be appreciated that similar compounds, other than those which have been specifically set forth hereinabove, may be utilized as shrinkproofing agents in the process of the present invention. Additionally, the shrinkproofing compositions used may be a mixture of one or more of the above compounds or other similar compounds which fall within the generic descriptions which have been given. Often, such mixtures will be the natural result of the preparation of the compositions, which preparations may give a statistical distribution of the possible products.

In preparing the impregnating solutions for use in the method of the present invention, the shrinkproofiing component as has been described is dispersed or dissolved in a suitable solvent. Although any solvent in which the modified isocyanate material will dissolve without decomposition may be used, in many instances, the aromatic organic solvents, such as benzene, toluene, xylene, and the like, are preferred. Additionally, halogenated aliphatic solvents, such as trichloroethylene, perchloroethylene, carbon tetrachloride, methylene chloride, and the like, have also been found to be extremely useful. The solvents may be classified generally as benzene, substituted benzenes containing 1 to 3 lower alkyl groups of 1 to 6 carbon atoms each and halogenated lower alkyls containing 1 to 6 carbon atoms and 1 to 8 halogens. The shrinkproofing component is dispersed or dissolved in the solvent in an amount sufficient to provide the desired resin add-on the proteinaceous material when the material is impregnated with the solution. Concentrations Within the range of about 0.5 to about 50 percent by weight of the solvent composition are typical, but in many instances, higher concentrations are also suitable, up to the maximum solubility of the modified isocyanate material in the solvent used. Typical of such higher concentrations which may be used are those of to percent by weight of the solvent composition or even higher, in those instances where the modified isocyanate material used is miscible in substantially all proportions with the solvent.

In preparing an impregnating solution for use in the present method, the diisocyanate may be dissolved in a suitable solvent as has been described above. Desirably, the solvent used is in an amount from about equal parts by weight to about 10 times by weight of the diisocyanate, with amounts within the range of about one to fi've times by weight being preferred. To the thus-formed solution of the diisocyanate there is added the polyhydroxy compound, the relative amounts of diisocyanate and polyhydroxy compounds being such as to provide the mole ratio of reactants as has been described hereinabove and form the desired polyhydroxy-modified diisocyanate. Typically, the reaction times and temperatures for effecting this modification are within the range of about 10 minutes to 3 hours at temperatures within the range of about 10 degrees centigrade to 80 degrees centigrade. Preferably, the times are from about minutes to 1.0 hour at temperatures from degrees centigrade to 50 degrees centigrade. As has been previously indicated, these products will con tain at least 3 free NCO groups.

Once the desired modified product is formed, additional solvent may be added to the reaction mixture to obtain the impregnating solution having the desired concentration. Alternatively, of course, the polyhydroxy-modified diisocyanates may be prepared separately and thereafter dissolved in the solvent in appropriate amounts to form the impregnating solution.

The proteinaceous material, such as a wool textile material, may be impregnated with the polymerizable shrinkproofing solution prepared as indicated hereinabove, using any convenient means. For example, the wool may be immersed or padded in the treating solution and the fabric then passed through squeeze rolls to remove excess solution. If desired, the treating solution may be applied to the material by spraying, rather than by immersion. Other suitable application techniques, as are known to those in the art, may also be used. After the proteinaceous materials have been impregnated with the solution, they are preferably dried so as to remove the solvent from the material. Desirably, the impregnation is carried out so that the treated proteinaceous material has a resin add-on within the range of about one to about 15 percent by weight of the material. Higher resin add-ons than 15 percent, e.g., to percent, may be attained in some instances although, generally, it has not been found that such higher add-ons appreciably improve the shrink resistance which is obtained. Generally, it has been found that resin add-ons appreciably less than 15 percent, e.g., 0.1 to 5 percent are often sufiicient to provide durable shrinkproofing of the proteinaceous materials. Typically, the treating solution is maintained at a temperature within the range of about 10 degrees centigrade to the boiling point of the solvent used, e.g., degrees centigrade for perchloroethylene, and preferably is within the range of about 20 degrees centigrade to about 30 degrees centigrade during the impregnation step. Thereafter, the impregnated material is dried, preferably in an oven, at a temperature within the range of about 20 degrees centigrade to the boiling point of the solvent used with temperatures within the range of about 65 degrees centigrade to about degrees centrigrade being preferred.

Following the impregnation and drying of the proteinaceous material, the thus-treated fabric is then cured in Water. Although various techniques may be utilized in effecting this Water cure, the treated proteinaceous material is preferably immersed in water and maintained in the water until the curing is complete.

It has been found that the time to effect the desired cure of the modified isocyanate material with which the proteinaceous textile is impregnated varies with the temperature at which the cure is effected. Accordingly, it is desirable that the water used is at an elevated temperature, temperatures within the range of about 40 degrees centigrade to about 100 degrees centigrade being typical, with temperatures within the range of about 80 degrees centigrade to about 94 degrees centigrade being preferred. When carrying out the water cure at these temperatures, curing times within the range of about one hour to about one minute are typical, with times of 30 minutes to two minutes being preferred. It is to be appreciated, that where the length of curing time is. not an important factor, the water cure of the modified isocyanate impregnant may be carried out at room temperature, i.e., about 20 degrees centigrade. Under such conditions, the curing time may be as long as several days, e.g., 48 hours. There is, however, some indication that the full shrinkproofing effectiveness of the modified isocyanate compositions may not be attained when the water cure is carried out under these low temperature conditions. Moreover, it has been found that low temperature curing techniques, and particularly those carried out below about 75 degrees centigrade, may not impart to the treated fabric the desired degree of durability to dry cleaning solvents, such as trichloroethylene. In many instances, after curing under these conditions, dry cleaning of the fabric may remove appreciable quantities of the cured shrinkproofing material so that after a subsequent laundering, shrinkage may occur. Additionally, it has been found that in some instances water in vapor form may be used to effect the cure of the treated fabric. Accordingly, low temperature curing techniques are generally not preferred.

It is to be further appreciated, that if desired, the Water cure of the modified isocyanate impregnant may be effected by substantially saturating the impregnated proteinaceous material with water and thereafter, completing the polymerization or cure of the modified isocyanate by heating the water-wet, substantially saturated material at an elevated temperature. In such processes, curing temperatures within the range of about 66 degrees centigrade to about 177 degrees centigrade for periods of about 30 minutes to about one minute are typical, with temperatures Within the range of about 107 degrees centigrade to about degrees centigrade for periods of 10 minutes to about three minutes being preferred. After the water cure of the impregnated textile material has been completed, the material is then dried to remove any water which may remain. Frequently, where the latter described curing process is used, i.e., Water impregnation of the treated fabric, followed by heating at an elevated temperature, the curing and drying of the fabric are effected substantially simultaneously.

It has been found that in many instances the water used to carry out the polymerization or cure of the modified isocyanate impregnant in the textile material is desirably slightly alkaline. Typical pH values for the curing water are within the range of about 7.5 to 9. Where the pH of the curing water is below these values, it may be adjusted by adding thereto an alkaline material, such as an alkali metal bicarbonate. Additionally, if desired, the curing water may also contain small amounts of a suitable wetting agent, to insure more thorough and rapid Wetting of the impregnated material. Typical wetting agents which may be used are nonionics, such as the polyalkylene ethers and anionics, such as alkyl aryl sulfonates and sulfates. These materials are typically present in amounts within the range up to about one percent by weight of the treating water, amounts within the range of about 0.05 to about 0.2 percent being preferred.

As has been indicated hereinabove, the process of the present invention may be carried out on proteinaceous materials in various forms, including yard goods, finished articles, such as sweaters and the like, as well as on the unspun fiber or the yarn itself. It has been found that proteinaceous textile materials, such as wool, which have been treated in accordance with this process consistently show an area shrinkage of less than about five percent, with area shrinkages within the range of about one to three percent being typical. Moreover it has been found that the shrink resistance is retained by the treated fabric even after numerous washings in hot water and that the hand and feel of the treated materials are not substantially different from those of untreated material. Additionally, the shrinkproof finish is durable to dry cleaning and is found to impart dimensional stability to the fabric. It also facilitates dyeing and improves dye fastness.

In order that those skilled in the art may better understand the present invention and the manner in which it may be practiced, the following specific examples are given. It is to be understood that these examples are illustrative of the invention and are not intended to be limitations thereon. In these examples, unless otherwise indicated, temperatures are in degress centigrade, parts and percentages are by weight and shrinkages are given as percent change from an untreated, unwashed control.

EXAMPLE 1 A textile treating composition was formed by dissolving 100 parts of toluene diisocyanate in 285 parts of trichloroethylene. To this solution was added 185 parts of castor oil and the resulting mixture was heated at 50 degrees centigrade for 30 minutes and then cooled to room temperature. The reaction mixture contained 0.575 mole of the isocyanate and 0.181 mole of castor oil. To the cooled reaction product there was added additional trichloroethylene to form two impregnating solutions containing 1.5 percent and 3.0 percent of the castor oil modified diisocyanate. These solutions were padded onto five ounce Worsted fabric to obtain a wet pick-up on the fabric of 150 percent in each case. The treated fabric was then dried in air to room temperature and cured by immersion in water for minutes at a temperature of about 70 degrees centigrade. The resin add-ons on the maintained within the range of degrees centigrade to degrees centigrade. Thereafter two treating solutions were formed from the reaction product by the addition of trichloroethylene, as in the previous example. These solutions contained 2.0 percent and 3.0 percent of the reaction product, respectively. Wool fabric was impregnated with these solutions as in Example 1. The impregnated samples were dried and then cured by immersing the fabric in water at room temperature to obtain a wet pick-up of about 100 percent and then heating the wet fabric for five minutes at about 120 degrees centigrade. The two treated samples were then washed as in Example 1 and the area shrinkage was found to be 4.4 percent and 1.3 percent as compared to an untreated control which had an area shrinkage of 76 percent.

EXAMPLE 3 The procedure of Example 1 was repeated using varying amounts of the castor oil and toluene diisocyanate to form the reaction product. Treating solutions containing 4.0 percent of each reaction product were prepared, as Well as solutions containing 4.0% of other isocyanates and these were padded onto wool fabric samples. These samples were then dried, cured and washed as in Example l and the area shrinkages measured. Using this procedure, the products used and the results obtained were as follows:

Reactants, parts by weight Free NCO Area groups per shrinkage, Toluene di- Castor Trichloromole of 4 percent isocyanate oil ethylene product solution Isocyanate used E CH3(CHz)14-mNCO 1 73. 3 F. Hcxarnethylenedlisoeyanate 2 71. 6 G Bis(4-1soeyanato-3-methoxyphenyl) methane 2 45. 2 H Toluene diisocyanate 2 69. 7 I Di(4-isoeyanatopheny1)methane 2 21. 5

The samples were then dried and the change in the area of the marked rectangle on each was measured, as well as the Gurley stiffness. Using this procedure, the following results were obtained:

Area Gurley shrinkage, stiffness,

percent milligrams Untreated sample 18 Sample treated with 1.5 percent solution... 0. 7 22 Sample treated with 3.0 percent solution. 0.7 36

It was also noted that the hand of the treated fabric was not significantly changed from that of the untreated sample.

EXAMPLE 2 A treating composition was formed as in Example 1 with the exception that the reactants used were as follows:

Parts Trimethylol propane 13.4 Toluene diisocyanate 52.2 Trichloroethylene 65.6

This gave a reaction mixture containing 0.1 mole of trimethylol propane and 0.3 mole of the diisocyanate. These reactants were heated to 45 degrees centigrade and then stirred for four hours while the temperature was From the above, it is seen that when the polyhydroxymodified diisocyanate products used contain less than 3 NCO groups per mole, there is a marked decrease in shrinkproofing effectiveness.

EXAMPLE 4 A Worsted wool fabric, bonded to acetate tricot, was treated with a 2.0 percent solution of a 3:1 toluene diisocyanate-castor oil product, formed as in Example 1, in methyl chloroform. The fabric was impregnated to a 180 percent wet pick-up and dried on steam heated cans at 105 degrees centigrade to 120 degrees centigrade. Curing of the impregnated fabric was effected by padding With water containing 0.1 percent sodium bicarbonate, the water solution being at a pH of 8.0 and a temperature of about degrees centigrade. The Wet fabric was held for ten minutes and was then padded through the water again and held for 15 minutes. After rinsing in water, the cured fabric was dried on cans at degrees centigrade to degrees centigrade. After five home washes, the treated fabric showed an area shrinkage of less than 2.0 percent. Additionally, after air drying or tumble drying, the washed fabric had a rating of 5 on the wash and Wear scale for wrinkle resistance, American Association of Textile Chemists and Colorists Test 88A1964T, wherein 5 is the best rating and 1 is the worst.

EXAMPLE 5 A treating solution was made up in methyl chloroform as in Example 4 using the same reaction product, with the exception that the solution contained 2.5 percent of the reaction product. This solution was padded on 100 yards of worsted fabric in a standard padder at five tons pressure to obtain a wet pick-up of about 157 percent. The impregnated fabric was then dried as in Example 4. The dried fabric was then divided into three portions. Two portions were cured by padding through hot water at about 80 degrees centigrade and pH 8 and batching on a rool for 1.5 hours. The cure of the third portion was effected by charging the cloth to a standard dye beck containing water at 70 degrees centigrade and pH 8. The cloth was run continuously through the beck for 15 minutes while the water temperature was maintained at 70 degrees centigrade. Thereafter, all three portions of cloth were squeezed and dried on steam heated cans at 105 degrees centigrade to 120 degrees centigrade. The fabric portion cured in the dye beck and one of the portions cured in the padder were washed for five hours as in Example 1 and the fol- The second padder cured portion of fabric Was then dyed with a conventional acid dye, Fast Crimson GR-l. The fabric was immersed for 1.5 hours in a two percent dye solution, pH 3, which was maintained at the boil. An untreated control sample was also included in the dye bath. It was noted that the treated fabric absorbed the dye more readily than the untreated and the final dye shade was deeper in the treated fabric. Additionally, the treated fabric showed percent area shrinkage during the dyeing process while the untreated control was felted and had an area shrinkage of about percent.

EXAMPLE 6 The procedure of Example 1 is repeated with treating solutions prepared by using the polyhydroxy compounds and diisocyanates in the amounts shown in the following table. In each instance, the reaction times and temperatures are varied as necessary to obtain the indicated reaction product. With all of these treating solutions, the W001 Solution A 13 Wet pickup (percent) 208 160 Solids add-on (percent) 9. 2 6. 9 Area shrinkage (percent) 5 washes 14.6 25. 6 10 washes 26. 6 37.6

While there have been described various embodiments of the invention, the compositions and methods described are not intended to be understood as limiting the scope of the invention, as changes therewithin are possible and it is intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principles may be utilized.

What is claimed is:

1. A method of sh-rinkproofing a woolen material which comprises contacting said woolen material with a polymerizable treating solution comprising a polyhydroxymodified isocyanate composition having from 3 to 6 free isocyanate groups per molecule, said polyhydroxy-modified isocyanate being the reaction product of a polyhydroxy compound containing from 3 to 6 hydroxyl groups and an organic diisocyanate, depositing a shrinkproofing amount of said isocyanate composition on said Woolen material and, thereafter, curing the thus-treated material with water at a temperature of at least about 66 degrees treated has an area shrinkage of less than about SIX percent. centrgrade.

Moles of Moles of Free NCO D 3" Diisoper mole Y Y cynate of reaction Sample Polyhydroxy compound compound Dhsocynate compound compound produc A 1.2,3,4,5,6hexane hexol 1 Alpha-naphthyl diisocynate 4 4 B Pentaerythritol 1 m-Phenylcnc diisocynate. 3 3 C Trimethylol heptadecane- 2 1,4cyclohoxylene diisocyanate. 6 3 D Erythrulose 1 Hexarnethylene diisocyanate 6 6 E Dextrose 1 4,4-diphenylpr0pane diisocyanate 3 3 F Glycerose disaccharide 1 3,3-dimethoxy-4,4' diphenylene diis0cyanate 4 4 G Sabinic acid triglyceride- 2 2,3-butylene diisocyanate 6 3 H. Aleurittc acid monoglyceride 1 Cyclopentylidene diisocyanate 4 4 1.- Jalapinolic acid triglyceridm 3 2,4-chlorophenyl diisocyanate 9 3 J. Trihydroxy n-butyrie acid. 1 3,3'-bitoluene-4,4diisocyanate. 3 3 K Hexahydroxy heptonic acid--. 2 1,5-naphthalene diisocyanate-. 6 3 L Idonic ac 1 Ethylidene diisocyanate 4 4 M Sorbitan monopalrnitate 1 Methylenc-bis-(4-pheny1 diisocyanate) 5 5 N 'Ietgakis (hydroxymethyl) phosphonium chlo- 1 Ethylene diisocyanate. 3 3

O Glycerol 1 2,6-t0luene diisocyanate 3 3 EXAMPLE 7 The following two solutions of a diol and a diisocyanate were prepared, having a total active solids content of 4.5% and a diolzdiisocyanate mole ratio of 1:1:

Solution A: Percent by weight A 12" x 16" swatch of 6 oz. all Woolen fabric was immersed in the treating solution, squeezed, and dried for 15 2. The method as claimed in claim 1 wherein the molar ratio of polyhydroxy compound to diisocyanate is from about 1:3 to about 1:6.

3. The method as claimed in claim 1 wherein the polyhydroxy-modified diisocyanate in the treating solution has the formula:

R-O(H3-N(RNG 0) wherein each R is independently selected from alkyl groups containing from 1 to 25 carbon atoms in a straight or branched chain or aralkyl groups containing from 8 to 30 carbon atoms in a straight or branched chain, and each R is independently selected from alkyl, alkaryl,

1 1 aralkyl or aryl groups containing from 6 to 40 carbon atoms, in a straight or branched chain.

4. The method as claimed in claim 3 wherein the modified isocyanate is contained in the treating solution in an amount within the range of from about one to about 50 percent by weight of said 'solution.

5. The method as claimed in claim 4 wherein the water cure is eifected at a temperature of from about 66 to about 177 degrees centigrade.

6. The method as claimed in claim 1 wherein the diisocyanate is toluene diisocyanate and the polyhydroxy compound is trimethylol propane.

7. The method as claimed in claim 6 wherein the treated material is cured with water at a temperature of from about 66 to 177 degrees centigrade for a period of from about 30 minutes to about one minute.

8. The method as claimed in claim 1 wherein the di isocyanate is toluene diisocyanate and the polyhydroxy compound is castor oil.

9. The method as claimed in claim 8 wherein the treated material is cured with water at a temperature of from about 66 to 177 degrees centigrade for a period of from about 30 minutes to about one minute.

10. A shrink-resistant woolen material produced in accordance with the method of claim 1.

11. A shrink-resistant woolen material produced in accordance with the method of claim 2.

12. A shrink-resistant woolen material produced in accordance with the method of claim 3.

13. A shrink-resistant woolen material produced in accordance with the method of claim 6.

14. A shrink-resistant woolen material produced in accordance with the method of claim 7.

15. A woolen material produced in accordance with the method of claim 8.

16. A shrink-resistant woolen material produced in accordance with the method of claim 9.

References Cited UNITED STATES PATENTS 3,093,441 6/1963 Whitfield et a1 1l714l X 3,384,506 5/ l968 Elkin 117-141 X 3,386,962 6/1968 Damusis ll7-161 X FOREIGN PATENTS 232,542 4/1958 Australia 11716l 908,188 4/1960 Great Britain 117-l 61 WILLIAM D. MARTIN, Primary Examiner H. J. GWINNELL, Assistant Examiner Patent No. 3.702.776 7 Dated mber 14.1972

Invento'r(s) ge M. Wagner It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2 line 59: 'acolho'ls should read--al-cohols-- Column 3 lines L6: should read---tr imethylol octane trimethylol nonene tr imethylol undecane trimethylol heptade'cane, 'trimethylol pr'opene trimethylol butene tr imethylol pentene glycerol, sorbit0l---.

Signed and sealed this 17th day of April 1973.

(SEAL) Attest:

EDWARD M.FLETCHER',JR. 7 7 ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents FORM PC4050 (10 69) uscoMM-Dc' 6Oa76-P69 a u.s. sbvnnuzmmanna omca as macs-an, 

